





PREPARATION OF A CYCLIC DIAZO COMPOUND 


BY 


COURTLAND LIVINGSTON BUTLER 
B.S., Pennsylvania State College, 1920 


THE LIBRARY GF THE 


ray 99 1098 
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UNIVERSITY OF ILLINOIS 


THESIS 


SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS 
FOR THE DEGREE OF MASTER OF SCIENCE IN CHEMISTRY 
IN THE GRADUATE SCHOOL OF THE UNIVERSITY 
OF ILLINOIS, 1923 


URBANA, ILLINOIS 


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i 
a ACKNOWLEDGEMENT 
Thanks sre due to Professor #. A. Noyes 
| 
for suggesting this problem and to frrofessor W. A. | 
Noyes and Dr. ©. 5S. Marvel for helpful suggestions | 
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received durine the course of this work. i 
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I. 
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IV. 


CONTENTS 


INTRODUCTION woesssvee cece ane eenwevesecens 
PROPOSED METHOD OF PREPARATION ...ccesens 
EXPERIMENTAL .....--00:5 bevver sean mer serene 
CONCLUSION con esccccencscvesvcevensesescee 


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penance RE ST eR TRS A ETT ES STAAL EST TEs | 


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Digitized by the Internet Archive 
In 2021 with funding from 
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https ://archive.org/details/preparationofcycOObutl 


1. INTRODUCTION 


Several attempts heave been made to prepnre optically 
active diazo compounds, with the sim of throwing some licht on the 
nature of positive and negative valences. CG. &. Marvel with 


We A ° Noye gh 


several years aro attempted to prepare various active 
diazo esters and failed. The only evidence of optical activity 
they obtained was this:-- on treating certain active amino ester 
hydrochlorides with nitrous acid, hydroxy acids were obtained which 
had &@ slight rotation. If the reaction goes thru the diazo stage, 
this is evidence of anasymmetric diszo molecule. HK. M. Chiles, 
with WwW. 4, Noyes” two years after the work of Marvel and Noyes, pub- | 
lished #® paper describing the prepsration of opticrlly active diazo 
compounds. Pive or eix were prepared in all. They point out the 
extreme exse with which these compounds racemise, and worked at low 


3 


temperstures and pressures to prevent this. Levene, in an article 


desling with hexossminic acids indicated the possibility of opticsll | 


active diazo compounds. He later reported optical activity* in 
the ease of diazo succinic ester prepsred from dextro scpartic ester, 


and in the cxses of the chloro and bromo derivatives prepsred by the 


S. Marvel with W. A. Noyes, J. A. GO. & 42, 2259 (1920) 

M. Chiles with W. A. Noyes. J. A. G. S. 44, 1798 (1922) 

A. Levene, J. Biol. Chem. 36, 89 (1918) 

A. Levene and L. A. Mikeska, J. Biol. Chem. 45, 593, (1921) 
" ” J. Biol. Chem. 52, 485, (1922) 





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action of HCl and HBr on the active diazo ester. Levene then 
attempted to prepsre * erystslline diazo compounat or 2 crystalline 
derivative of a diazo compound which would have 2 high rotstion. 
He succeeded in prepsring 2 bromo di-ethyl succinate by the action 
of HBr on ethyl diazo succinate in ‘ very pure state. This com- 
pound gave a rotation of about 60°. Levene showed that this high 
rotation could not come from any impurity and claims this is suffi- 
cient evidence to show conclusively that the carbon atom of the 
diazo grouping is asymmetric. 

All attempts thus far in this field have been carried out 
in the open chain series of compounds. It wes thought that a 
cyclic diazo compound mircht possibly be more stable, and that being 
& heavier molecule would be more apt to be crystalline, and there- 


fore be more lisble to sive positive results than an open chain 


diazo compound. It was decided to try to prepare 4 compound of the 


structure 








This could be eslled diazo (2) cyclo hexanone dicarboxylic ester 
Pied} « 





lp, A. Levene and lL. A. Mikesks, J. Biol. Chem. 55, 795, (1923) 


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If. PROPOSED METHODS OF PREPARATION 


geveral methods of prepsring dizso (2) syclo hexanone 


mR 


ie COpH ao oH Hp 5a 
NE, Ae H» HNHGOC .H,. 


dicarboxylic exter (1,1) were a 


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COpH C0 ,C5Hs 
HNHCOCgHg =- Hy HIHCOC .H. HH» 
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Ae 2 
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Resolution of VI to s pure ad or 1, form 


OeCoks 
COoCpus 


og =N=N 


&e HKeduction of methyl eslicylute to the hexs hydro compound oxids- 
tion to the ketone ester, which would contain an active hydrocen 

atom; subetitution of -c G OR by means of codium ethylate followed 
by chloresrbonic ester; treatment with hydroxyl smine snd reduction 


RRNA NS A ELAN INLD NON NE 


le asear-Sohn, Arbeite Methoden furoreiniseh-chemische Laboratorien, 
1907 ed. pp. 362-265. 


ey A, Noyes, Oreanic Chemistry for the Leboratory (1920) »o. 205. 
by 
Js VOn Braun, Ber. 42, 859. (1909) 





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of the oxime to the amino compound; resolution; diazotization. 

3. Reduction of anthranilic acid; bromination and preparation of 
the Grignard compounds; treatment with COg to form the dicarboxy 
compound; resolution; diszotization. 

4. Condensation of delta brom valeryl aldehyde with melonic ester 
and preparation of the diazo compound from the ketone dicarboxy 
ester thus formed 2s in (2). 

5. Condensation of pimelic ester to hexa2none carboxylic ester and 


subsequent treatment ss in (2). 


It was foreseen that the preparation of the compound by 
method (1) above would be difficult when it came to putting in the 
second carboxyl group. There is chance that, on trestment of the 
brominated hexa hydro snthranilic seid with KCN, HBr will eplit out 
giving an unsaturated compound. There ®re two possibilities ss to 
which way this reaction would go -+ 


C oH, oH 
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OH-COOH SHCOOH 
| si | faa Ras | 
JN, C-NH, O=NH+HOH C=0+NH,, 


oh, on, Co 


This could be checked up as follows:- If the splitting out of HBr 


occurred as in {1), the carbon stom to which the amino group is 
attached would still be asymmetric “ni work on the compound could be 
continued; if it occurred as in (2) an unstable molecule would be 
formed which in water solution would react as indicated sivine the 
ketone 2cid. Work on this compound would then have to be discon- 


tinued. 





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Another difficulty to be expected is the fact that hexs 
hydro anthranilic acid is o Pamine acid and is therefore apt to 
lose NH, very easily. 

| If work must be discontinued on derivatives of hexa hydro 


anthrenilic xcid, it is proposed to sttempt to prepare similar 

















-gompounds stertine with m-amino benzoic cid. This compound on 
reduction should give 2 gamma amino seid, which would be more stable 
than the beta acid. 
After substitution of the second carboxyl croup, the diazo | 
compound might be prepared by the method of Gurtius* or if this 
failed, by thet of Oppe” since the gamma acid should easily close 
the ring and form a lactam. From the lactam a nitroso derivative 
could be prepared which on decomposition with slkali should yield a 


diazo compound. 


00H S00 COOH / COOH 
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iH, Hi, CH, oHy » CHy ole | —> te CHy 
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} aaioncmmnicine ee’ saaee a : —- N— Ns l, _ ste i co 
H——CHNH, CHg——-CH-NH = Cy —-GH—-I-N=0 OH —Q =N=N 


In attempting the first step in the prepsration of the 





compound VII shown on p2ge 3, eatalytic reduction of anthranilic 


acid was first tried. Platinum oxide wae precipitated as described 








by Adams and VYorhees” to be used as catalyst. This method eave 





1 assar-Cohn, 1907 Hd., Part 2, page 227. 


e oppe, Bere 46, 1095 (1913) 








S,dams and Vorhees, J. A. . 3. June, 1922. 


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negative results, the reason probably being that the conditions 
most favorable to catnlytic reduction were not determined. The 
method will later be studied more fully. 

Reduction by means of sodium and amyl alcohol was found 
to be a2 fairly satisfactory method. Ginhorn and Meyenberg* 
reduced anthranilic 2cid 2nd claimed to have obtained 60% of the 
theory 2s hexthydro anthrenilic ethyl ester. Carrying out exactly 
their directions in regard to the reduction but isolating the 
benzoyl derivative” of the reduced seid instend of the ethyl ester 
of the free acid resulted in yields of from 8.6% to 9.2% in several 
runs. If the sodium is added rapidly -- within half en hour for a 
run of 10 geme. -- instead of over & period of three hours as 
directed by Hinhorn and Meyenberg, the yield is incressed to from 
40% to 50% for 10 gm runs. Subsequent runs using 25 gms. 2nd 50 gms} 


of anthrenilic acid gave yields of only 30% 2s the benzoyl derivative 
of the reduced anthranilic scid. 


: 
This is as far as the work has been carried starting with | 
anthranilic acid. 

A little has been done on catalytic reduction of methyl 
salicylate. This compound gives = mixture on catelytic reduction. 
There was not enough reduced material prepared for separation and 
identification. It is possible thst after reduction water splits 
off giving 2n unsaturated compound, which in turn is reduced making 


the end-product methyl ester of hexahydrobenzoic acid. 


leinhorn and Meyenberg, Bere 27, 2470. 
fzull and @ernsheim, A. 295, 202. 


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Itl. EXPERIMENTAL 


I Preparstion of anthranilic acid hydrochloride and attempt to 
reduce this compound eatalyticslly in water and in alcoholic 
solutions. 

Anthraniliec seid from stock room 100 ems. 

Alcohol 400 Ge Gs 
This solution was digested with animal charcoal and filtered. The 


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solution was then poured into 2 liters of cold weter and the an- 


thranilic scid thus precipiteted out. ‘The precipitate was filtered 


| 
and dried. | 
Recovered enthraniliec acid 83 ems. 
The stock room anthrenilic ecid is thus sbout 83% pure. 
To make the hydrochloride, purified anthranilic acid wos 
dissolved in ether and precipitated out with dried HCl gas. 
In the attempted reduction, the following rune were mede. 


the time for 211 runs wis twenty-four hours. 


(1) Anthranilie acid hydrochloride, 0.1 mole = 17.3 Gms. 


Water 100 Ge Ge 
Catalyst 0.20 ems. 
A% room temperature, with hydrogen at 25 pounds, no change 
in the resding of the pressure gauge was observed, hence 
there was no absorption of hydrogen. 

(2). Anthranilie acid hydrochloride, 0.1 mole = 17.3 gms. 
Water 100 Gs. Ge 
Catalyst 0.30 gms.e 


No absorption of hydrozen could be detected. 


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(3) Anthranilic scid hydrochloride, 0.1 mole = 17.3 ems. 
Aleohol -- 95% 100 co. «a. 
Catalyst 0.25 gms. 


No reduction. 


Il Prep2ration of methyl anthranilate hydrochloride and attempted 
reduction in water solution. 
fhe hydrochloride was mede 2s for anthranilic acid by 


precipitation from ether solution with HCl eas. 


Runs corresponding to those made on anthranilic acid hydro-j 


chloride were made, 411 sivine nesative results. 


Lilt Preparetion of Benzoyl derivetive of hexehydro snthranilic seid 

The materials ond proportions used were those of Binhorn 
and Meyenbere. 

Anthranilic seid 10 ems. 

amyl aleohol 400 Ge Gs 

Sodium 52 2MSs 

the anthranilic cid wee dissolved in amyl alcohol in a 
one-liter round bottom flask, connected with » reflux condenser, 
the solution heated to boiling #nd the sodium sdded as fast as the 
resction permitted. The mixture was refluxed until 411 the sodium 
was digested, the time required being about one and one-half hours. 

The amyl 2lcohol solution wes then extracted with weter 
to remove the sodium sslts of hexs hydro benzoic, pimelic, and 
hexs hydro anthranilic scids. The alkexline aqueous solution was 


extracted with ether to remove amyl alcohol, and the lsst of the 












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ether removed from the solution on the steam cone. The solution 





was then scidified, precipitating the hexshydro benzoic, and pimelic 





acids, whichwere extracted with ether. The &queous solution was 





made alkaline and treated with benzoyl chloride, in an smount 





corresponding to 60% yield of hexa hydro anthranilic acid (Schotten- 
a4 









Bauman Keaction After completion of the reaction, the solution 









was filtered and acidified, precipitating out the benzoyl derivatives 
of hexs hydro xnthranilic scid and of unchenzed anthranilic seid, 





and benzoic cid. The solution was then filtered sand sucked as dry 





as possible on a Buehner funnel. The mixture of acids was next 







placed in =: beaker end just enouch boiling dilute slecohol (alcohol 






three volumes, water two volumes) was added to dissolve it. on 


eooling, the pure benzoyl derivative of hexs hydro anthrenilic acid 






(li. P. 220-222°) crystallized out in needles, leaving the other 





materials in solution. Subsequent fractions did not show any benzoyl 





derivative of hexa hydro enthranilic acid. 






Following “inhorn and Meyenberg'’s directions and adding 






the sodium to the amyl @lcohol solution of anthranilic scid, slowly 






over # period of three hours gave the following results: 





Run 1. Anthranilic s¢id (stock room) 15 ems. 







Benzoyl derivative of hexshydro snthranilic acid 2 oMSe 


Theoreties!] yield 






% yield 







Correeted for purity of orizinal snthranilic scid 


luassar-Cohn, Ed, 1907, Part 2, 34. 






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Anthranilic acid (store room) 10. gms. 
Benzoyl derivative of hexahydro anthranilic acid 1.4 em. 
Theoretical yield 18 gms. 
Per cent yield 7.7 
Gorrected 9.2% 
Anthranilic ecid (store room) 50 ems. 
Benzoyl derivative hexahydro anthranilic acid 7.0 gome. 
Theoretical yield 90 gme. 
Per cent yield 7.7 


Corrected 9.2% 


. Addition of sodium 3s rapidly ss the violence of the 
reaction would permit eave the following results; 
1. Anthranilic scid (stock room) 10 ems. | 


Benzoyl derivative of hexahydro anthranilic acid 7.5 gms 


Theoretical yield 18 ems. 


% yield corrected 50.6% 
Anthranilic scid 10 ams. | 
Senzoyl derivative hexshydro anthranilic acid 

Theoretiesl] yield 18 ems. 
% yield corrected 43.3% 
Anthranilic seid 25 ems. 5O ems. 


Benzoyl derivetive of hexa 
hydro anthranilic acid 1 om. 23 gms. | 


Theoretiosl yield 45 2mse 90 ems. 


% yield corrected 30% 30% 





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ls Uneneceseful attempte to reduce anthrenilie acid ond 


methyl anthranilste esatalytically with hydrosen ueing platinum “s 
estelyet have been mide. 

Be In attempting to reduce methyl es lieyisate to hexs hydro 
methyl exlicylate eatulytically, it wae found thet a mixture 
resulted. Thie wae not separated. 

Be The benzoyl derivetive of hexs hydro snthrenilic acid was 
prepared in yields varying from 30% to 60% depending on the amount 
of miterie] need. fhe method used modifiee thet of Sinhorn ond 
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to the amyl “lcoholic solution of snthranilio seid, snd the end 
product isolated. 


















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BIBLIOGRA PHY 


G. S. Marvel with W. 4. Noyes. J. £4. 0. 3. 42, 2259 (1920) 
EH. M. Chiles with W. A. Noyes. J. 4. 0. 3. 44, 1789 (1922) 
Levene, P. A. J. Biol. Chem. 36, 89, (1918) 
Levene, P. A. ond Mikeske, L. A.,J. Biol. Chem. 45, 593 (1921) 
’ " A Ss 52, 485 (1922) 
' : ‘ 55, 795 (1923) 
J. von Braun, Ber. 42, 839 (1909) 
Lassar-Cohn, Arbeits Methoden, 1907 Hd. Part 2, 362-365 
" " " 227 
E 4 34 
W. A. Noyes, Org. Chem. for the saborstory (1920) 205 
Oppe, Ber. 46, 1095, (1913) 


Adams and Vorhees, J. 4. 0. 5S. June, 1922 


Einhorn and Meyenberg, Ber. 27, 2470. 


Bull and Gernsheim, A. 295, 202. 














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